Lubricating composition



Faienteei Apr. 22, 1947 LUBRICATING COMPOSITION John M. Musselman, SouthEuclid, Ohio, assignor to The Standard Oil Company, Cleveland, Ohio, acorporation of Ohio No Drawing. Application November 13, 1945, SerialNo. 628,382

13 Claims. (Cl. 252-32-7) It has been suggested to add oxidizedpetroleum acids to lubricating oil in an effort to increase theoiliness. While afiording some result in this direction, the oxidationacids have had the very serious drawback of greatly accelerating thebreakdown of the oil, particularly if elevated temperatures were,involved. In accordance with the present invention it now becomespossible to at tain the desired advantages of oxidized petroleummaterial with in addition a remarkable stability and other propertiesnot heretofore regarded as possible with such starting material.

To the accomplishment of the foregoing and related ends, the invention,then, comprises the features hereinafter fully described, andparticularly pointed out in the claims, the following descriptionsetting forth in detail certain illustrative embodiments of theinvention, these being indicative however, of but a few of the variousways in which the principle of the invention may be employed.

The invention will be best understood by reference to an illustrativeexample: 7

Paramn wax is oxidized under pressure to yield in combination with theoxidation product. The

nature of the phosphorus in the reaction product is not known, but itdoes not appear to be present as a thiophosphate because the phosphoruscontent is materially-reduced upon reaction with an alkali in the mannerdescribed subsequently.

The reaction is carried out simply by mixing the reaction ingredients intheproportions stated at the temperature stated. Preferably thepentasulphide is added in increments to a kettle containing theoxygenated hydrocarbon and the reaction mass is stirred. It is completedin 1 to 4 hours when the exothermic reaction subsides.

an oxidation product comprising hydroxy acids.

Desirably, this is separated into saponiflable and non-saponifiablefractions, and the further procedure'is carried out with thesaponifiable fraction, although where preferred the non-saponifiablediluent material may be left in. Phosphorus 3o pentasulphide is reactedupon the oxidation product by heating to a temperature abovethiophosphate formation, i. e., at least about 275 F. and preferably toaround 300 F. An exothermic reaction takes place and it is generally notnecessary to exceed a temperature above 425 F. It is particularlydesirableto employ such an amount of phosphorus pentasulphide asrequisite to supplant the oxygen of the compound with sulphur. In otherwords the amount of the phosphorus pentasulphide should be such that thesulphur therein is stoichiometrically sufiicient to replace all of theoxygen in the oxygenated hydrocarbon. The amount of the sulphide to beusedcan be calculated readily, depending on the oxygenated hydrocarbonand its oxygen content. About 20 percent of phosphorus pentasulphide issatisfactory for an oxidized paraflin wax having about 7% oxygen. Theamount generally falls within the range of 14 to per cent for oxygenated5 By next subjecting the material to air-blowing. residual odors may beeliminated.

Then, if desired, the material may be converted into a metal compound,and for instance from the saponification number of the material therequired amount of lime for saponification is indicated and may beadded. It is advisable that the product so formed be around 9-11 pHvalue. The product has outstanding lubricating and stabilizingproperties and ability to maintain metal surfaces in clean polishedcondition. If desired, only a part of the product of the reaction.product of the pentasulphide with the oxygenated hydrocarbon may beconverted into the metal compound so as to form a mixture of the initialreaction product and the metal compound thereof.

The initial reaction product of the phosphorus sulphide and theoxygenated hydrocarbon, or the metal compound formed therefrom may bein-' corporated in a mineral lubricating oil in various amounts toimprove the properties of the lubricating oil depending upon theparticular purpose for which the oil is to be used. In general an amountof at least 0.1 per cent will be used. Inasmuch as the reaction productsare lubricants themselves there is no upper limit but in general theamount will not exceed 10 per cent.

thereof, oxidized polymers of butylene or isobutylene and other olefins,naphthenic acids, or other oxygenated hydrocarbons derived by oxidizingpetroleum hydrocarbons and containing oxygen capable of being displacedwith sulphur by reaction with a sulphide of phosphorus. The oxidationmay be carried out in the liquid or vapor phase, as in the case of theoxidation of paraflin wax discussed earlier, and in a manner well knownin the art. (See chapter 36 of Ellis: The Chemistry of PetroleumDerivatives.) These oxidation products used in accordance with theinventions are liquids or solids, preferably having a boiling pointabove the temperature of the reaction with the sulphide so as to avoidthe use of pressure during the reaction, and comprise mixtures of acids,alcohols, esters, aldehydes, ketones, lactones and similar oxygencontaining hydrocarbon compounds. These mixtures are very complex andpossess unique properties which are not inherent in any sing econstituent thereof. The oxidation product may be separated into aaponiflable fraction as in the case of oxidized paraflin wax, or thenon-saponifiable portion may be left in.

The neutralization or saponification of the product from the reaction ofphosphorus pentasulphide and oxidized petroleum may be eflected also byother bases, such as aluminum, tin, zinc, lead, magnesium, barium,potassium, sodium, ammonia, amines, or a mixture of two or more of them,such as calcium and barium, aluminum and calcium, etc.

As illustrating the characteristics of the present compounds,comparisons in operating results with an untreated oil, an oilcontaining parafiin oxidation acid, an oil containing the calcium saltof paraffin oxidation acid, and an oil containing a compound inaccordance with the present invention, may be noted: The testing enginewas an Ethyl Gasoline Corporation test engine and it was operated inaccordance with Procedure IV, namely, running at 1200 revolutions perminute, with sump temperature 300 F., and jacket temperature 212 F., andan iron catalyst in the amount of 0.1%, F203 as iron naphthenate. Thefuel was a high octane gasoline containing 3 cc. of lead tetraethyl pergallon. The operating re- 4 metal compound, the following example isalso included:

An oxidized parafdn wax, available under the name of "A101: 152" wasreacted with 25% phosphorus penta'sulphide, which amount is thattheoretically required to replace .the oxygen in this oxidized parailinwax. The reaction was carried out at 300 F. for one hour. The reactionproduct was separated from the sludge. The reaction product was found,upon analysis, to contain 1.87% phosphorus and 9.92% sulphur. It wastested in accordance with procedure IV explained earlier, with thefollowing results, using the identical oil in each instance.

The reaction products of the invention are to be distinguished fromreaction products obtained by reacting elemental sulphur and compoundsyielding sulphur, such as sulphur halides, with oxygen containingcompounds, since in such a reaction the oxygen is not replaced in themanner in which it is in accordance with the invention. The reactionproducts of the invention are also to be distinguished from the use ofother sulphides in smaller amounts less than that in which the sulphurof the sulphide is the stoichiometric equivalent of the oxygen to bereplaced. All such reaction products are inferior to the reactionproduct of the invention and not the equivalent thereof.

I claim:

1. A new lubricating oil composition of matter comprising a majorportion of a lubricating oil and an amount of an additive sufficient toimprove the stability of the lubricating oil, said additive comprisingthe metal compound of the reaction product of an oxygenated petroleumhydrocarbon boiling above the hereinafter named reaction temperature andan amount of phosphorus pentasulphide within the range of 14 to 30% andat least stoichiometrically sufficient to supplant the oxygen of theoxygenated petroleum hydrocarbon with sulphur, reacted at a temperaturewithin the range of 275 to 425 F. to form a reaction product separablefrom a sludge sults beingcomprising the major part of the phosphorus inSame plus 3% San. plus 3% Same plus 37 S. A. E. 20 Midcalcium salt ofoxidized paraicalcium salt of Continent Oil fin oxidizeiiid1parafreaction product Hours Operation 20 20 2 60. Per cent Sludge- 5.0-7.0- 8.0- 0.9. Acid number 2.5 2.0- 1.9- 0.6. Viscosity Inerpasa 150 270228 94. Mg. lacquer per sq. dem. pistcn. .0. 85.0. 69.0.-. 0. Condition0! Engine Light sludge Heavy sludge-.- Heavy sludge.-. No sludge.

For a continuous running test of twenty hours, it is thu seen that theoriginal oil had a life of actually less than twenty hours forsatisfactory lubrication, and that'the addition of oxidized paraflin orof the calcium salt of oxidized paramn did not materially aid, while themetal salt of the reaction product gave outstandingly good performance.

As illustrative of the properties of the initial the pentasulphide, andsubsequently converted into said metal compound.

2. A new lubricating oil composition of matter comprising a majorportion of a lubricating oil and an amount of an additive sufficient toimprove the stability of the lubricating oil, said additive comprisingthe alkaline earth metal compound of the reaction product of anoxygenated petroleum hydrocarbon boiling above the hereinreactionproduct before its conversion into a 7 after named reaction temperatureand an amount of phosphorus pentasulphide within the range of 14 to 80%and at least stoichiometrically suilicient to supplant the oxygen of theoxygenated petroleum hydrocarbon with sulphur. reacted at a temperaturewithin the range oi 275 to 425 F. to form a reaction product separablefrom a sludge comprising the major part of the phosphorus in thepentasulphide, and subsequently converted into said alkaline earth metalcompound.

3. A new lubricating oil composition of matter comprising a majorportion of a lubricating oil and an amount of an additive suflicient toimprove the stability of the lubricating oil, said additive comprisingthe metal compound reaction product of an oxidized parafiln wax and anamount of phosphorus pentasulphide within the range of 14 to 30% and atleast stoichiometrically suflicient to supplant the oxygen of theoxidized parai'fln wax with sulphur, reacted at a temperature within therange of 275 to 425 F. to form a reaction product separable from a.sludge comprising the major part of the phosphorus in the pentasulphide,and subsequently converted into said metal compound.

4. A new lubricating oil composition of matter comprising a majorportion of a lubricating oil and an amount of an additive sufiicient toimprove the stability of the lubricating oil, said additive comprisingthe alkaline earth metal compound of the reaction product of an oxidizedparaflln wax and about 20% phosphorus pentasulphide reacted at atemperature of about 300 F., said amount of phosphorus pentasulphide andsaid temperature resulting in a reaction product separable from a sludgecomprising the major part of the phosphorus in the pentasulphide, andsubsequently converted into the alkaline earth metal compound.

5. A new lubricating oil composition of matter comprising a, majorportion of a lubricating oil and an amount of an additive suflicient toimprove the stability of the lubricating oil, said adsupplant the oxygenof the oxidized paraflln was with sulphur, reacted at a temperaturewithin the range of 275 to 425 F. to form a reaction product separablefrom a sludge comprising the mtaijor part of the phosphorus in thepentasulp de.

8. A new lubricating oil composition of matter comprising a majorportion of a lubricating oil and an amount of an additive sufficient toimprove the stability of the lubricating oil, said additive comprisingthe reaction product of an oxidized parafiin wax and about phosphoruspentasulphide, reacted at a temperature of about 300 F., said amount ofphosphorus pentasulphide and said temperature resulting in a reactionproduct separable from a sludge comprising the major part of thephosphorus in the pentasulphide.

ditive comprising the calcium compound of the reaction product of anoxidized paraffin wax and about 20% phosphorus pentasulphide, reacted ata temperature of about 300 F., said amount of phosphorus pentasulphideand said temperature resulting in a reaction product separable from asludge comprising the major part of the phosphorus in the pentasulphide;and subsequently converted into the calcium compound.

6. A new lubricating oil composition of matter comprising a majorportion of a lubricating oil and an amount of an additive suiilcient toimprove the stability of the lubricating oil, said additive comprisingthe reaction product of an oxygenated petroleum hydrocarbon boilingabove the hereinafter named reaction temperature and an amount ofphosphorus pentasulphide within the range of 14 to 30% and at leaststoichiometrically suflicient to supplant the oxygen of the oxygenatedpetroleum hydrocarbon with sulphur, reacted at a temperature within therange of 275 to 425 F. to form a reaction product separable from asludge comprising the major part of the phosphorus in the pentasulphide.

'7. A new lubricating oil composition of matter comprising a majorportion of a lubricating oil and an amount of an additive sufiicientto-improve the stability of the lubricating oil, said additivecomprising the reaction product of an oxidized paraffln wax and anamount of the phosphorus pentasulphide within the range 01 14 to 30% andat least stoichiometrically suflicient to 9. An additive effective insmall amounts for improving the stability of a lubricating oil,comprising the metal compound of the reaction product of an oxygenatedpetroleum hydrocarbon boiling .above the hereinafter named reactiontemperature and an amount of phosphorus pentasulphide Within the rangeof 14 to 30%, and at least stoichiometrically suflicient to supplant theoxygen of the oxygenated petroleum hydrocarbon with sulphur, reacted ata temperature within the range of 275 to 425 F. to form a reactionproduct separable from a sludge comprising the major part of thephosphorus in the pentasulphide, and subsequently converted into saidmetal compound.

10. An additive effective for improving the stability of a lubricatingoil, comprising the alkaline earth metal compound of the reactionproduct of an oxygenated petroleum hydrocarbon boiling above thehereinafter named reaction temperature and an amount of phosphoruspentasulphide within rthe range of 14 to 30% and at leaststoichiometrically sufficient to supplant the oxygen of the oxygenatedpetroleum hydrocarbon with sulphur, reacted at a temperature with-=- inthe range of 275 to 425 F. to form a reaction product separable from asludge comprising the major. part of the phosphorus in thepentasulphide, and subsequently converted into said alkaline earth metalcompound.

11; An additive efiective for improving the stability of a lubricatingoil, comprising the calcium compound of the reaction product of anoxidized parafiin Wax and about 20% phosphorus pentasulphide reacted ata temperature of about 300 F., said amount of phosphorus pentasulphideand said temperature resulting in a reaction product separable from asludge comprising the major part of the phosphorus in the pentasulphide,and subsequently converted into said calcium compound.

12. An additive efiective for improving the stability of a lubricatingoil, comprising the reaction product of an oxygenated petroleumhydrocarbon boiling above the hereinafter named reaction temperature andan amount of phosphorus pentasulphide within the range of 14 to 30% andat least stoichiometrically suflicient to supplant the oxygen of theoxygenated petroleum hydrocarbon with sulphur, reacted at a temperaturewithin the range of 275 to 425 F. to form a reaction product separablefrom a sludge comprising the major part of the phosphorus in thepentasulphide.

13. A new composition of matter, suitable for use as an addition agentto improve the characted at a temperature within the range of 275 to 425F. and with stolchiometrically sufllcient phosphorus pentasulphide tosupplant oxygen of the oxygenated petroleum hydrocarbon with sulphur andto separate the major part of the 5 phosphorus from the reactionproduct.

JOHN M. MUSSELMAN.

REFERENCES The following references are of record in the 10 file of thispatent:

UNITED STATES PATENTS Number Name Date 1,987,397 Gallsworthy Jan. 8,1935 15 Number

